Blue anthraquinone acid dyes

ABSTRACT

COMPOUNDS, USEFUL IN THE DYEING OF POLYAMIDES, HAVING THE FORMULA:   1-NH2,2-(M-O3S-),4-((4-(((M-OOC-),R3-PHENYL)-SO3-),R1,R2-   PHENYL)-NH-)ANTHRAQUINONE   WHEREIN M REPRESENTS -H, -NA, -K, -LI OR NH4; R1 AND R2 ARE -H OR -LOWER ALKYL; R3 IS -H, -LOWER ALKYL, -F, -CL, BR OR NO2.

United States Patent Ice Patented May 28, 1974 Suitable aminophenolswhich can be used for reaction 3,813,402 with Bromamine acid to producethe intermediate having BLUE ANTHRAQUINONE ACID DYES th st ture I JamesF. Feeman, Wyomissing, Pa., assignor to Compton & Knowles Corporation,Worcester, Mass. $03M No Drawing. Filed Oct. 20, 1971, Ser. No. 190,8165 Int. Cl. C09b 1/34 US. Cl. 260-372 2 Claims ABSTRACT OF THE DISCLOSURE10 Compounds, useful in the dyeing of polyamides, having the formula:(Structure I) $03M R1 R include 3 H2N H para-aminophenol,

2-methyl-4-aminophenol, R1 002M 3-methyl-4-aminophenol,

2-ethyl-4-aminophenol,

3-ethyl-4-aminophenol,

2,3dimethyl-4-aminophenol, wherein M represents H, -Na, K, Li or NH.,;3,5-dimethY1-4-amifl0PheI101, R and R are H or -lower alkyl; R; is H,1ower 2,5-dimethyl-4-aminophenol,

alkyl, F, Cl, Br or N0 and the like.

Suitable chlorosulfonyl-benzoic acids which can be used This inventionrelates to new compounds that are usefor reaction with Structure Iintermediates to produce the ful in the dyeing of polyamides such asnylon, silk and new dyes include wool and that are particularly usefulfor the dyeing of the deeper dyeing nylon components ofdifIerential-dye- 3-chlorosulfonyl-benwic acid, ing nylon textiles. 3O4-chlorosulfonyl-benzoic acid,

The new compounds have the structure 2,4,5 or6-methyl-3chlorosulfonyl-benzoic acid,

SOQM R2 2,4,5 or 6-chloro-3-chlorosulfony1-benzoic acid,

R3 4-bromo-3chlorosulfonyl-benzoic acid,5-nitro-3-chlorosulfonyl-benzoic acid,

5 4-fluoro-3chlorosulfonyl-benzoic acid, 0: R1 002MZ-fluoro-S-chlorosulfonyl-benzoic acid;

- 2-chloro-4-ch1orosulfonyl-benzoic acid, 3chloro-4-chlorosulfonylbenzoic acid,

2 or 3-methyl-4-ch1orosulfonyl-benzoic acid, wherein and the like.

M represents H, ---Na, K, Li or NH The new com ound are useful s l'ht-fast blue d es R represents H or -lower alkyl; p s a lg y forpolyamides. When applied to yarns or textile fabrics R2 represents H orlower alkyl; composed of polyamides that have differing dyeing char- R3represents H, lower alkyl Br or acteristics, for example composite nylonyarns or textiles The new compounds are made by condensing l-aminocompoof tW0 or more different yp of nylon fibers4-bromoanthraquinone-Z-sulfonic acid (Bromamine acid) that havedifiering dyeing characteristics eg regular under mildly alkalineconditions in the presence of a copnylon, deep dyeing nylon, ultra-deepdyeing nylon, lightper catalyst with 4-amino-phenol, a4-amino-alkyl-phenol, dyeing nylon and cationic-dyeable nylon, the dyescan be or a 4-amino-dialkyl-phenol and reacting the thu for d used toproduce striking color contrasts between the difintermediate with achlorosulfonyl-benzoic acid or an alferent fiber types of a givencomposite by controlling the kyl, nitro or halo derivative thereof, alsounder mildly pH at which the dye is applied. In addition the dyes ofalkaline conditions. this invention may be applied simultaneously withdyes or The dyes are usually formed as the sodium salts of the othertypes such as disperse, modified basic, or neutral sulfonic andcarboxylic acids. They can be used as such dyeing acid dyes to givestill other contrast variants. Genor converted to the free acids 'bytreatment with an inerally, the dyes of this invention dye thedeeper-dyeing organic acid in the cold and filtering. These can beconnylons well at all usual pH values, e.g. from pH 2-11;

verted to various salts such as the Na, -K, Li or however, at pH valuesabove about 7 they do not dye NH, salt by neutralization with a suitablehydroxide, regular, light-dyeing or cationic dyeable nylonappreciacarbonate or bicarbonate. bly, and at pH 9+ do not dye thesecomponents at all.

When the compounds of this invention are applied to a composite nylonyarn or textile containing nylon 6 fibers and nylon 6,6 fibers, gooddiiferential dyeing is obtained between the nylon 6 and nylon 6,6fibers, different depths of blue color being obtained. The ratio ofdepth of shade between the two types of nylon and the exhaustion of thedyebath is dependent upon the pH value of the dyebath. In general,degree of exhaustion will decrease with increase of pH and regular orlight dyeing nylon 6,6 will be dyed in lighter shades or even be undyedwhile the more receptive components will be deeply colored thusproducing contrast.

The new compounds are compatible with a wide variety of other dyes forpolyamides when applied from a common bath, and in general they are notreadily blocked by other dyes.

The following example will serve to illustrate the preparation and useof the dyes of this invention. In this example, parts and percentagesare by weight and temperatures and in degrees centigrade, unlessotherwise stated.

(prepared by condensing lamino-4-bromoanthraquinone- Z-sulfonic acid,sodium salt, with para-aminophenol in alkaline solution in the presenceof CuCO as catalyst) was dissolved at pH 9.4 in 500 parts of water at75". To this solution was added 30 parts of sodium carbonate. During thenext half hour 35 parts of 3-chlorosulfonyl-benzoic acid was added insmall portions at the end of which the original greenish-blue solutionhad changed to reddish-blue. To the solution was added 90 parts ofsodium chloride. Upon cooling to 45 the product crystallized fromsolution and was filtered and dried.

It is a dark blue, highly water-soluble solid which dyes nylon and othernatural and synthetic polyamide fibers from aqueous acidic baths inreddish-blue shades having good fastness to light and washing and hasthe structure:

It dyes deep-dyeing and ultra deep-dyeing nylon fibers and fabrics fromneutral to alkaline baths while leaving regular nylon 6,6 undyed or onlyslightly tinted in the same bath.

The disodium salt (25 parts) was pasted into 250 parts of water givingcomplete solution at 25. Addition of 10 HzN parts of concentratedhydrochloric acid lowered the pH to less than 1 and gave completeprecipitation of the dye as the free acid. The precipitate was filteredand washed with parts of water containing 5 parts of concentratedhydrochloric acid. The resultant paste was slurried in 100 parts ofwater. Addition of 8 parts of concentrated ammonium hydroxide gave asolution of the dye as the diammonium salt at pH 10.

In the above procedure when the slurry of acid paste was treated with 5parts of potassium carbonate, a solution of the dipotassium salt of thedye resulted. Similarly, substitution of 5 parts of lithium carbonatefor the potassium carbonate gave a solution of the dilithium salt of thedye. These salts were obtained as dry water-soluble powders by spraydrying. They have similar dyeing and fastness properties to those of thedisodium salts when applied to nylon fibers and fabrics.

Dyes having a generally similar structure but which do not include awater-solubilizing group such as a carboxy group in the terminal benzenering do not have the dyeing characteristics of the dyes of thisinvention, in that they dye regular nylon from neutral to alkalinesolutions whereas the dyes of this invention are not satisfactory dyesunder such conditions.

wherein M represents H, --Na, K, Li or NH.;; R represents H or loweralkyl; R represents H or -lower alkyl; R represents H, lower alkyl, -F,Cl, Br or N0 2. A compound according to claim 1 having the structure:

References Cited UNITED STATES PATENTS 9/1940 Fleischhauer 260-372LORRAINE A. WEINBERGER, Primary Examiner E. I. SKELLY, AssistantExaminer U.S. Cl. X.R. 8-21 B, 39

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,813,402 Dated May 97'- James F. Feeman It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 2, Line 53 "or" should read --of-- Column 4 the Structure inClaim 1 appearing between lines 26 and 35 should appear as:

Signer? and sealed this 15th ay o April 1375'.

Attest:

C lL-IRSI-IALL DA?! 2-1 1: "my: n j j a mu ya on; o. III-ow.Commissioner of :atents Attesting Gfficer and Trademark FORM PO-IOSO (1069) USCOMM-DC 6O376-P69 ".5. GOVERNMENT PRINTING OFFICE III 0-866-S84.

